CN102775326B - A kind of method reducing inactivation of hydroxylamine inorganic liquid - Google Patents
A kind of method reducing inactivation of hydroxylamine inorganic liquid Download PDFInfo
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- CN102775326B CN102775326B CN201210277452.5A CN201210277452A CN102775326B CN 102775326 B CN102775326 B CN 102775326B CN 201210277452 A CN201210277452 A CN 201210277452A CN 102775326 B CN102775326 B CN 102775326B
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- inorganic liquid
- hydroxylamine
- strainer
- azanol
- absorption tower
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Abstract
The present invention relates to a kind of method reducing inactivation of hydroxylamine inorganic liquid, after the toluene-cyclohexanone-oxime solution being rich in impurity enters azanol oximate device hydroxylamine inorganic liquid system, thus it is active to reduce hydroxylamine inorganic liquid, absorption tower charging stock tank → pump → strainer → absorption tower charging stock tank hydroxylamine inorganic liquid circularly purifying flow process is set for this reason, the strainer that activated carbon of sorbent is housed is set, continuous filtration and purification are implemented to hydroxylamine inorganic liquid.By carrying out charcoal absorption purification to hydroxylamine inorganic liquid in the charging stock tank of absorption tower, plant capacity returns to 90% from 70% after contaminated, and the toluene reduced after polluting impacts hydroxylamine inorganic liquid activity, effectively ensures hydroxylamine catalyst activity and selectivity.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind of method reducing inactivation of hydroxylamine inorganic liquid, particularly reduce the method for inactivation of hydroxylamine inorganic liquid when azanol oximate prepares cyclohexanone-oxime.
Background technology
Hexanolactam is a kind of important Organic Chemicals, is mainly used to manufacture polymeric amide-6 fiber, also can be used for manufacturing polycaprolactam engineering plastics.Hexanolactam is obtained through Beckmann rearrangement by cyclohexanone-oxime.The main preparation methods of current cyclohexanone-oxime has azanol oximate method and oximes method.
Azanol oximate device is the core position of azanol oximate legal system for cyclohexanone-oxime, and main task produces the intermediates-cyclohexanone-oxime of hexanolactam, and its main raw material(s) is hydrogen, liquefied ammonia etc.But hydrogen source-coal device for producing hydrogen is due to problems such as, atures of coal, frequent parking causes hydrogen supply to interrupt for a long time, and azanol oximate device is also forced to stop.Part producing business is owing to having azanol oximate and oximes two cover production equipments, for balanced production load, when azanol oximate is stopped, for ensureing that follow-up workshop section does not stop, oximes product toluene-cyclohexanone-oxime is sealed in the washing FF of azanol oximate, with toluene-cyclohexanone-oxime that alternative azanol oximate device is self-produced, supply subsequent handling.But be rich in impurity because oximes device produces toluene-cyclohexanone-oxime, the toluene therefrom reclaimed, be re-used as extraction agent to extract the organic impurity in azanol oximate inorganic-liquid, effect of extracting is poor, the activity of inorganic-liquid and selectivity are declined to a great extent, and finally cause hydroxylamine catalyst activity and selectivity to decline to a great extent, have a strong impact on device and produce, reduce device and produce load.
At present, oximes device toluene cyclohexanone-oxime system and azanol oximate device toluene cyclohexanone-oxime system are gone here and there mutually and are run, and then affect the problem of hydroxylamine inorganic liquid activity, do not have Patents technical literature to use for reference reference at present.
The present invention carries out technological innovation to azanol oximate device toluene-cyclohexanone-oxime organic system; reduce the by-product impurities of oximes device toluene-oxime as far as possible to azanol oximate device toluene-cyclohexanone-oxime systematic influence; the toluene reduced after polluting impacts hydroxylamine inorganic liquid activity, protects hydroxylamine catalyst activity and selectivity.
Summary of the invention
The object of the invention is to provide a kind of method reducing hydroxylamine inorganic liquid activity; improve azanol oximate device toluene-cyclohexanone-oxime organic system; reduce the by-product impurities of oximes device toluene-cyclohexanone-oxime as far as possible to the pollution of azanol oximate device toluene system; the toluene reduced after polluting impacts hydroxylamine inorganic liquid activity, protection hydroxylamine catalyst activity and selectivity.
After entering azanol oximate device toluene-cyclohexanone-oxime organic system for oximes device toluene-oxime, contaminated toluene causes azanol oximate device hydroxylamine inorganic liquid activity decrease, for guaranteeing hydroxylamine inorganic liquid and catalyst activity and selectivity, take the hydroxylamine inorganic liquid activity and selectivity of trace analysis absorption tower charging stock tank, the strainer of configuration activated carbon is set, utilize activated carbon adsorption conversion characteristic, set up absorption tower charging stock tank → pump → strainer → absorption tower charging stock tank hydroxylamine inorganic liquid circularly purifying flow process, during hydroxylamine inorganic liquid is filtered, filter pressure 0.1 ~ 0.2MPa, temperature 40 ~ 50 DEG C, filtration cycle is 20 ~ 30 days, within 20 ~ 30 days, change an activated carbon.
Toluene-oxime the solution being rich in impurity of the present invention is the standby toluene-cyclohexanone-oxime solution of oximes legal system.
Hydroxylamine inorganic liquid of the present invention is composed as follows:
H
+ ：1-7 mmol/g；
NH
3OH
+：0.05-1.3 mmol/g；
PO
4 3-：1.0-3 mmol/g；
NH
4 +：0.2-3.5 mmol/g。
Activated carbon of sorbent of the present invention is 4 μm-6 μm.
Strainer of the present invention is the spent catalyst strainer in the hydroxylamine inorganic liquid recycle system.
Inversely, filter pressure is higher for filter pressure and inorganic-liquid flow, and inorganic-liquid flow is lower, and vice versa.For controlling filter pressure is 0.1-0.2MPa, adjustment means are exactly the inorganic-liquid flow regulating turnover strainer, and when inlet flow rate is certain, adjustment filter outlet flow is with setting pressure.The present invention monthly adds 500 ~ 1000kg, 4 μm of-6 μm of activated carbon to strainer, and filtering traffic is 5-7 m
3/ h.
Positively effect of the present invention is:
By carrying out charcoal absorption purification to hydroxylamine inorganic liquid in the charging stock tank of absorption tower, plant capacity returns to 90% from 70% after contaminated.Monthly add 500 ~ 1000kg, 4 μm of-6 μm of activated carbon to strainer, carry out activated carbon adsorption purification to hydroxylamine inorganic liquid in the charging stock tank of absorption tower, current production effect improves obviously.And active carbon filtration of the present invention does not need newly added equipment, utilize existing waste catalyst recovery equipment just can realize inorganic-liquid purification, method is simple, obvious processing effect.
Embodiment
Below in conjunction with example, the present invention will be further described, but be not limitation of the invention further.
Example 1:
500-1000kg 4 μm of-6 μm of activated carbon are added to spent catalyst strainer, spent catalyst filter pressure is 0.1MPa, temperature 40 DEG C, form activated carbon filter cake, set up absorption tower charging stock tank → pump → spent catalyst strainer → absorption tower charging stock tank hydroxylamine inorganic liquid circularly purifying flow process, filter after 7 days, analyze the activity and selectivity of hydroxylamine inorganic liquid, result is as follows:
| Hydroxylamine inorganic liquid index | Active (%) | Selectivity (%) |
| Before not filtering | 14.67 | 79.52 |
| Filter after 7 days | 15.62 | 76.24 |
Example 2:
500-1000kg 4 μm of-6 μm of activated carbon are added to spent catalyst strainer, spent catalyst filter pressure is 0.2Mpa, temperature 50 C, form activated carbon filter cake, set up absorption tower charging stock tank → pump → spent catalyst strainer → absorption tower charging stock tank hydroxylamine inorganic liquid circularly purifying flow process, filter after 7 days, analyze the activity and selectivity of hydroxylamine inorganic liquid, result is as follows:
| Hydroxylamine inorganic liquid index | Active (%) | Selectivity (%) |
| Before not filtering | 14.67 | 79.52 |
| Filter after 7 days | 16.15 | 77.39 |
In hydroxylamine inorganic liquid there is slight decomposition in azanol, is decomposed into NO
xand N
2o, temperature, pressure slightly rises.
Example 3:
500-1000kg 4 μm of-6 μm of activated carbon are added to spent catalyst strainer, configuration activated carbon filter cake, utilize charcoal absorption conversion characteristic, set up absorption tower charging stock tank → pump → spent catalyst strainer → absorption tower charging stock tank hydroxylamine inorganic liquid circularly purifying flow process, spent catalyst filter pressure is 0.15MPa, temperature 45 C, filter cake balanced condition, recurrent state is stablized, and period is analyzed the activity and selectivity of a hydroxylamine inorganic liquid point different time sections, and result is as follows:
| Hydroxylamine inorganic liquid index | Active (%) | Selectivity (%) |
| Before not filtering | 14.67 | 79.52 |
| Filter after 7 days | 17.60 | 75.73 |
| Filter after 25 days | 21.25 | 82.64 |
Filter 25 days, hydroxylamine inorganic liquid activity and selectivity recovers normal level.
Therefore determine that optimum filtration cycle is 20 ~ 30 days according to this, spent catalyst filter pressure 0.1 ~ 0.2MPa, temperature 40 ~ 50 DEG C, within every 20 ~ 30 days, change an activated carbon, move in circles, and according to above data, after explanation starts filtration, the activity of hydroxylamine inorganic liquid is improved significantly.
Embodiment of the present invention is only the description carried out the preferred embodiment of the present invention; not design of the present invention and scope are limited; under the prerequisite not departing from design philosophy of the present invention; the various modification that in this area, engineering technical personnel make technical scheme of the present invention and improvement; protection scope of the present invention all should be fallen into; the technology contents of request protection of the present invention, all records in detail in the claims.
Claims (8)
1. one kind is reduced the method for azanol inorganic process liquor inactivation, after the toluene being rich in impurity-cyclohexanone-oxime solution that oximes legal system is standby enters azanol oximate device azanol inorganic process liquor system, thus it is active to reduce azanol inorganic process liquor, absorption tower charging stock tank → pump → strainer → absorption tower charging stock tank azanol inorganic process liquor circularly purifying flow process is set, it is characterized in that arranging the strainer that activated carbon of sorbent is housed, continuous filtration and purification are implemented to azanol inorganic process liquor.
2. method according to claim 1, is characterized in that described azanol inorganic process liquor consists of:
H
+ ：1-7 mmol/g；
NH
3OH
+：0.05-1.3 mmol/g；
PO
4 3-：1.0-3 mmol/g；
NH
4 +：0.2-3.5 mmol/g。
3. method according to claim 1, is characterized in that described strainer is the spent catalyst strainer in azanol inorganic process fluid circulation.
4. method according to claim 1, is characterized in that described activated carbon of sorbent size is 4 ~ 6 μm.
5. method according to claim 1, is characterized in that changing once for activated carbon of sorbent 20-30 days of configuration in described strainer.
6. method according to claim 1, is characterized in that described filter pressure 0.1 ~ 0.2MPa.
7. method according to claim 1, it is characterized in that described filter temperature controls is 40 ~ 50 DEG C.
8. method according to claim 1, is characterized in that described azanol inorganic process flow quantity is 5-7 m
3/ h.
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|---|---|---|---|
| CN201210277452.5A CN102775326B (en) | 2012-08-07 | 2012-08-07 | A kind of method reducing inactivation of hydroxylamine inorganic liquid |
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|---|---|---|---|
| CN201210277452.5A CN102775326B (en) | 2012-08-07 | 2012-08-07 | A kind of method reducing inactivation of hydroxylamine inorganic liquid |
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|---|---|
| CN102775326A CN102775326A (en) | 2012-11-14 |
| CN102775326B true CN102775326B (en) | 2015-08-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87107162A (en) * | 1987-10-24 | 1988-05-18 | 河南省郸城县生物化工厂 | Non-crystallizing process for producing lactic acid |
| CN101224880A (en) * | 2007-01-16 | 2008-07-23 | 中国石油化学工业开发股份有限公司 | Hydroxylamine-oximation circulatoing system |
| WO2010142841A1 (en) * | 2009-06-11 | 2010-12-16 | Outotec Oyj | Method and apparatus for regeneration of extraction solution in metal extraction processes |
| CN102030606A (en) * | 2010-12-06 | 2011-04-27 | 黄石振华化工有限公司 | Processing method for removing pyridine compound from coal coking crude benzene by fixed bed supplemental refining and hydrorefining processing |
-
2012
- 2012-08-07 CN CN201210277452.5A patent/CN102775326B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87107162A (en) * | 1987-10-24 | 1988-05-18 | 河南省郸城县生物化工厂 | Non-crystallizing process for producing lactic acid |
| CN101224880A (en) * | 2007-01-16 | 2008-07-23 | 中国石油化学工业开发股份有限公司 | Hydroxylamine-oximation circulatoing system |
| WO2010142841A1 (en) * | 2009-06-11 | 2010-12-16 | Outotec Oyj | Method and apparatus for regeneration of extraction solution in metal extraction processes |
| CN102030606A (en) * | 2010-12-06 | 2011-04-27 | 黄石振华化工有限公司 | Processing method for removing pyridine compound from coal coking crude benzene by fixed bed supplemental refining and hydrorefining processing |
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|---|---|
| CN102775326A (en) | 2012-11-14 |
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